Welcome to the CLU-IN Internet Seminar

1
Welcome to the CLU-IN Internet Seminar

• Use of Nanomaterials for Environmental
  Remediation of Hazardous Waste Sites The Role of
  Nanoinformatics in Support of State Agencies'
  Health and Safety Oversight ActionsSponsored by
  U.S. EPA, Office of Superfund Remediation and
  Technology InnovationDelivered May 21, 2012,
  200 PM - 330 PM, EDT (1800-1930 GMT)
• InstructorDr. Ephraim Massawe, Southeastern
  Louisiana University (ephraim.massawe_at_selu.edu)Mo
  deratorJean Balent, U.S. EPA, Technology
  Innovation and Field Services Division
  (balent.jean_at_epa.gov)

1
Visit the Clean Up Information Network online at
www.cluin.org
2
Housekeeping

• Please mute your phone lines, Do NOT put this
  call on hold
• QA
• Turn off any pop-up blockers
• Move through slides using links on left or
  buttons
• This event is being recorded
• Archives accessed for free http//cluin.org/live/a
  rchive/

2
3
Presented at the U.S. Environmental Protection
Agency Contaminated Site Clean-Up Information
Seminar - CLUIN
Use of Nanomaterials for Environmental
Remediation of Hazardous Waste Sites The Role of
Nanoinformatics in Support of State Agencies'
Health and Safety Oversight Actions
May 21st, 2012

• Dr. Ephraim Massawe
• Southeastern Louisiana University

4
Nanoremediation or nano-enhanced environmental
remediation defined

• Nanoremediation (nano-enhanced remediation)
  defined
• A method or technique employing nanomaterials to
• Decontaminate or detoxify contaminants
• Reinstate land or ecosystem to original state

5
Examples of environmental and other related
applications of nanomaterials

TiO2 Pigments, UV-absorber, catalyst

ZnO Polymer filler, UV-absorber

Au, Fe, Ag Remediation, clothing

CeO2 / Ce2O3 Catalyst (cars), fuel additive

ZrO2 Ceramic, catalyst support

Quantum dots CdSe/ ZnS/ InAs/ InP/InGaP Medical imaging, drug delivery
6
Specific application of nanomaterials in
remediation
Nanomaterials Examples Remediation Uses
BNPs and Zero-valent Iron Ni gold Pd or Pt BNPs - Bimetallic Nano Particles nZVI Remediation of waters, sediments or Soils (hydrocarbons)
Metal oxide ENPs TiO2 ZnO and Cerium Oxide (CeO) Remediation of waters, sediments or Soils (hydrocarbons)
Nano Metals Engineered Nanosilver (Ag) Remediation of waters, sediments or Soils (hydrocarbons)
Carbonaceous ENPs Multiwalled Carbon Nanotubes MWCNTs-much better than activated C Sorption of metals e.g. Cd Pb Cu etc.
Carbonaceous ENPs Multiwalled Carbon Nanotubes MWCNTs-much better than activated C Sorption of BTEX compounds
Carbonaceous ENPs Nanoporous Activated C Fibers (ACFs) Sorption of BTEX compounds
Nano Clays/ Zeolites Na6Al6.Si1O.12H2O Sorption/Ion Exchange for metals
Carbon-based Dendrimers Hyper-branched polymers (1-20 nm) PAHs Ultra-filtration of heavy metals
7
Nanoparticles - Definition

• According to the American Society for Testing
  Materials (ASTM) standard definition
  nanoparticles includes
• A nanoparticle is one whose length is measured in
  nanometers (10-9 m) and
• Range from 1 to 100 nm in two or three dimensions
• At this size nanomaterials poses properties
  including large surface area, and other novel
  chemical, physical, and biological properties
  which are distinctly different from larger (bulk)
  particles of similar chemical composition.

Source ASTM International (2006) Terminology for
Nanotechnology, ASTM E 2456-06.
8
Various Types of Nanomaterials!
Anthropogenic or Engineered NPs Incidental Particles from Natural Particles from
Carbon-based Nanotubes, Fullerenes Metal Oxides Quantum Dots Nanotubes Nanowires Dendrimers Combustion products Industrial Processes Vehicles emissions Construction Plants, Trees Oceans, other water bodies Erosion Dust
9
Why this project Introduction

• Thousands of hazardous waste sites in the country
  are known as superfund sites, regulated by the
  U.S. EPA
• Some of the hazardous wastes deposited in the
  Superfund sites can be persistent,
  bioaccumulative and toxic (PBT)
• Traditional remediation techniques can be costly,
  and may take a very a long time
• Nano-enhanced remediation is fast, cost-effective
  and a promising technique of conducting clean-up
  operations

10
What is a Superfund Site?

• A Superfund site is an uncontrolled or abandoned
  place where hazardous waste is located
• Contaminants from the sites can affect
  remediation workers, nearby community, general
  public and environment.
• Superfund is a federal program
• Implemented under the Comprehensive Environmental
  Response, Contamination and Liability Act
  (CERCLA-1980).
• Nearly 1200 superfund sites require immediate
  clean up.

11
Superfund sites are the high risk part of a
larger problem
Site Owner of Sites age
National Priority List (NPL) superfund sites 740 lt1
Other superfund sites 500 lt1
States and private companies 150,000 51
Civilian agencies 3,000 1
Department of Energy / DOD 12,000 4
Underground Storage Tanks (UST) contaminated sites 125,000 43
Resource Conservation and Recovery Act (RCRA) 3,800 1
Total Sites 295,000 100
12
Chemistry or Process GoverningNano-enhanced
Environmental Remediation
Process Exploited Nanomaterials used Target compounds
Photocatalysis TiO2 Organic pollutants

Adsorption Iron oxides, dendrimers Metals, organic compounds, arsenic

Redox reactions Nanoscale zero-valent iron (nZVI), nanoscale calcium peroxide Halogenated organic compounds, metals, nitrate, arsenate, oil
Ref Mueller, N.C. and Nowack, B (Elements, Vol.
6, pp. 395400
13
Chemistry of Nanoremediation of TCE with nZVI

• Reactive surface coatings (e.g. Pd Pt Cu Ni
  or Ag doping)
• High surface areas (e.g., 150 m2/gm)
• nZVI Redox is 25-30 x faster than bulk iron

14
Economic Incentives for Nano-enhanced Remediation
(Cost Comparison Per Site) - reference
Remediation Technology Cost of Remediation ()
Traditional remediation methods using pump and treat (without nano-enhancement) 5,000, 000
Traditional remediation methods e.g. permeable reactive barriers (PRBs) 3,400,000
Nano-enhanced remediation methods using nano-zero valent iron (nZVI) 600,000
Traditional remediation methods or technologies
are costly and may take as many as 40 years to
clean up all sites across the United States
15
Nano-Informatics Project Background

• Nanotechnology and nanomaterials research and
  development have reached an advanced stage of
  commercializing, and various applications are
  currently documented
• Nanomaterials use for environmental remediation
  applications has been successfully reported by
  the U.S. EPA in their superfund sites
• Exposures to engineered nanoparticles have the
  potential to cause significant ecological and
  safety impacts as well health effects in
  laboratory animals and cells
• Scientific community is concerned about
  environmental, health, and safety risks
  associated with the handling of nanomaterials

16
Nano-Informatics Project Background (continued)

• Past examples of materials that emerged as good
  for various applications such as DDT and PCBs,
  were confirmed to be deadly. This precedent
  cannot be repeated for nanomaterials!
• Since nanomaterials in workplace in particular
  and in the environmental in particular remains
  largely unregulated, a precautionary approach
  based on information available
• A precautionary approach is voluntary, and
  nano-specific EHS oversight mechanisms would be
  prudent to account for the unique characteristics
  of the materials.

17
Nano-Informatics Project Background Why
nanoinformatics project?

• Collect and collate information and technological
  relevant to nanomaterials to enhance the
  capability of state agencies and programs to
  better anticipate, recognize, evaluate, control,
  and confirm potential EHS hazards associated
  with nanomaterial in all applications, including
  environmental remediation

Hoover, M.D., T. Armstrong, T. Blodgett, A.K.
Fleeger, P.W. Logan, B. McArthur, and P.J.
Middendorf Confirming Our IH Decision-Making
Framework, The Synergist, 22(1) 10, 2011.
18
Information related issues for consideration
Progress Toward Safe Nanotechnology in
the Workplace A Report from the
NIOSH Nanotechnology Research Center
http//www.cdc.gov/niosh/docs/2010-104/pdfs/2010-1
04.pdf (04-16-2012)
19
Working hypotheses to evaluate information needs
for EHS professional work and oversight
Existing Information and Scientific Knowledge Sufficient New Information and Scientific Knowledge Is Perhaps Needed
Traditional Remediation ? ???
Nano-enhanced Remediation ? ???
Output Product A Compendium of Information Relevant to Various Professions Working with Nanomaterials A Compendium of Information Relevant to Various Professions Working with Nanomaterials
Information Needs
Technological Needs
20
A framework for understanding information needs
for regulatory and oversight actions during
nanoremediation
Identify and evaluate
Traditional Remediation
Nano-enhanced Remediation
Anticipate and recognize
Evaluation methods
Information Needs
Control and Confirm
21
Nano-information related issues of consideration
Safety issues
Fig 1.0 Nanoscale zero-valent iron may ignite
spontaneously when it comes into contact with air.
22
Information on physicochemical properties and
other concerns in nano-enhanced remediation
In all the three treatment methods Described how
do physicochemical properties being
transformed?
Fig 2.0 In situ technologies used to treat
polluted groundwater and soils (1) injection of
nZVI to form a reactive barrier (2) injection of
mobile nZVI to form an nZVI plume (3)
incorporation of NP into topsoil to adsorb or
degrade pollutants
23
Information on physicochemical properties and
other concerns in nano-enhanced remediation
Fig 3.0 Mixing station where the iron particles
in the slurry are re-suspended before injection.
24
Information on physicochemical properties and
other concerns in nano-enhanced remediation
Fig 4.0 nZVI slurry being poured into a well.
25
Nanoremediation the roles of EHS professionals

• There has been a great interest of the scientific
  community in nano-enhanced remediation
• A large amount of information related to
  environmental remediation case studies has been
  generated.
• Not so well structured to help with the IH work
  of exposure or risk assessment studies or
  epidemiology etc
• There is need for structuring the available
  documents and tools and organize the information

26
Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce   Communication and Education Message and Audience Planning Tool for Understanding Information Needs of Various Professionals , Regulators for Safety and Health Protection of Nano-Remediation Workforce  
Workers Health and Safety Practitioners Management Policy Makers and Regulators Insurance/Lenders Raw Material RD Manufacturing Liability Education and Training Students Media Consumers Society/Ethical Issues Emergency Response (Police/Fire)
Literacy/Critical Thinking
Real-Life Examples
Understanding practices
Continuous Improvement
Modeling/Sharing
Assessment
Focus
Information
Information required or provided by various
stakeholders - Nanoinformatics 2020 Roadmap,
Hoover, M.D, 2011.
27
Information availability and accessibility at
the federal level

• Currently limited or no nano specific standards
  exist
• NIOSHs REL TiO2 (Ultrafine 0.3 mg/m3) (fine 2.4
  µg/m3).
• ENPs are chemical substances under TSCA
  (Statute)
• Premanufacture Notifications (100 PRN received by
  EPA for various ENPs
• Significant New Use Rule (SNUR) 5(a)(2) TSCA
  appropriate reviews needed by EPA for any
  manufacture, import or processing (Significant
  New Use Notice SNUN to be submitted 90 days
  before activity begins)
• Information gathering rule - 8 TSCA
  production volume, methods of manufacture and
  processing, exposure and release information, and
  available health and safety data. -
  http//www.epa.gov/opptintr/chemtest/pubs/sect8a.h
  tml
• http//www.epa.gov/oppt/nano/

28
Nano-related information for EHS oversight
availability and accessibility at the federal
level

• Test rule TSCA 4 ENPs on the market to be
  tested - http//www.epa.gov/oppt/chemtest/pubs/sct
  4rule.html
• ENPs may be regulated under CAA (statute) or
  U.S.EPA 40 CFR part 50 (National Ambient Air
  Quality Standards) if they endanger workers and
  public health.
• In this case, the role of the state governments
  will be to develop and implement SIPs, if the
  sites are close to urban centers or large cities

29
Nano-related information for EHS oversight
availability and accessibility at the federal
level

• EHS (occupational and non-occupational) risks
• Nanomaterials be wastes in water effluents or
  discharges air contaminants or water run off
• Currently, no Maximum Contaminant Levels (MCL)
  for ENPS
• If airborne, ENPs may cover large areas and
  impact public health
• Discharge of the ENPs into water bodies may
  require special permits under CWA. States
  enforce regulations
• Health effects (reproductive, developmental etc.)

30
Concerns for state government agencies and
programs in nano-enhanced remediation

• States may need to issue permits/licenses to
  contractors vendors or transporters of ENPs
  inspect or audit and enforce SH plans or
  programs
• OSHA has approved SH plans for 21 states to
  enable them enforce standards e.g. HAZWOPER
• State governments will play a key role to protect
  EHS across RD manufacture transport use and
  disposal of the ENPs, the need for relevant
  information is important!

31
Readiness of state agencies to regulate
synthesis, transportation, use and disposal of
ENPs

• Although not closely related to nano-enhanced
  remediation, the city of Cambridge, MA requires
• Inventories of ENPs manufacturing or handling
  facilities
• Share technical advise with other stakeholders
• Share EHS updates with workers and communities
• Track RD activities
• Track status of regulations and best work
  practices and
• Review changes in regulatory landscape every 2
  years

32
Nanoinformatics and EHS oversight What are the
relevant metrics of exposure?

• Sampling and measurements of ENPs - too small to
  sample or measure?
• Do state have the capability?
• Exposure and health risk measurements and
  estimations?
• Detection of contamination levels as airborne or
  waterborne
• Standardized operating protocols OSHE, NIOSH,
  EPA etc.
• Control of contamination to acceptable levels
  airborne or waterborne
• ENPs better substitutes based on technical
  efficiency? Time? Cost?
• Engineering control? - Glove box? Conventional
  hoods? LEVs? GEV?
• Administrative control?
• Selection of PPEs if we cant measure, we cant
  manage - how do we promote proper selection if
  without sampling or measurements?

33
Nanoinformatics and EHS oversight What are the
relevant metrics of exposure?

• 4. Metrics to evaluate biological effects what
  would these be?
• Particle size?
• Particle shape?
• Oxidant generation?
• Surface functionality?
• Rate of dissolution?
• 5. Other physical and chemical properties of the
  ENPs solubility, pH etc -
• 6. What is the dominating chemistry? And the dose
  response relationship?

These five parameters are believed to important
determinant of exposure vs. biological response
34
Exposure and Health Risks Assessments

• Risk Hazard x Concentration (Exposure)
• Do we need to redefine hazards of nanomaterials
  in the absence of exposure measurements
• Chemical properties to be taken into account
• Surface area
• size, shape, solubility, brittleness, aspect
  ratio
• Toxicity Info short-and long-term cumulative
  effects
• Genetic Changes up or down regulation
• Mass or concentration or computational models
  to predict distribution of particles within each
  biological compartment or use of the Monte-Carlo
  simulation models

35
Flow diagram for a framework to understand the
information needs of the state agencies
Site Characterization Does the site use ENPs?
Number of Workers Potentially Exposed (skills,
age, gender work practices etc)?
Potential for ENPs to contaminate water? air
soils? public health concerns epidemiological
surveillance, monitoring and disease registry?
Relevant information on chemical characteristics,
EHS measurements (methods and sampling
protocols)
Risk Assessment and Scoring
Risk Management
36
Conclusion

• Health and safety of workers handling ENPs can be
  enhanced by accessing relevant information
• Researchers, scientists, manufacturers, vendors
  can provide the information if the needs are
  known
• Some states are doing something other states may
  not. Many professionals need to work together to
  capture the information necessary to protect
  public and workers health and safety
• .

37
Conclusion

• Availability, access and sharing of information
  will lead to enhanced technical capability of all
  states in addressing EHS issues of ENPs!
• Survey questions to state agencies were based on
  this framework.
• Preliminary analysis of the responses received
  from agencies and programs across the country
  indicate that there is urgent need of information
  related to nanomaterials
• Information on EHS,
• Toxicity measurements and evaluation, and
• EHS regulatory framework, including exposure
  standards.

38
Conclusion

• Public health and workers safety and health can
  be protected by limiting exposures to ENPs and
  other nanoparticles through precautionary
  approach and oversight mechanisms
• This can be done by generating information
  necessary to set up standards and regulatory
  framework - based on science and relevant
  information
• At federal level a lot of work has been done,
  standards described non-legally binding some
  states have on-going activities other states do
  not.
• Set up of Site Exposure Matrix (SEM) similar to
  the DOEs and DOL for Radiation Sites
  ENPs/Health effects/Job Categories/Exposure/Risks
  

39
Thank You!
Dr. Ephraim Massawe, Southeastern Louisiana University OSHE Program SLU 10847, Hammond, LA 70402 Tel [phone] Fax [phone] Email ephraim.massawe_at_selu.edu
Acknowledgement LA-Board of Regent, Grant
LEQSF(2011) -Pfund-256 NSF - Experimental
Program to Stimulate Competitive Research (EPSCoR)
Q A
40
Resources Feedback

• To view a complete list of resources for this
  seminar, please visit the Additional Resources
• Please complete the Feedback Form to help ensure
  events like this are offered in the future

Need confirmation of your participation
today? Fill out the feedback form and check box
for confirmation email.
40
41
New Ways to stay connected!

• Follow CLU-IN on Facebook, LinkedIn, or Twitter
• https//www.facebook.com/EPACleanUpTech
• https//twitter.com/!/EPACleanUpTech
• http//www.linkedin.com/groups/Clean-Up-Informatio
  n-Network-CLUIN-4405740